Mild oxidation of tosylmethylisocyanide to tosylmethylisocyanate: utility in synthetic and medicinal chemistry

Abstract

A convenient and efficient (one-step) oxidation is reported of commercially available tosylmethylisocyanide (TOSMIC) to form tosylmethylisocyanate, making this highly reactive bifunctional molecule a readily available synthetic reagent. Besides engaging in nucleophilic addition reactions with alcohols, amines and thiols, tosylmethylisocyanate also reacts with carboxylic acids to form tosylmethylamides, which undergo substitution reactions in the presence of organocopper and organomagnesium reagents.

Arylsulfonylmethyl isocyanides: a novel paradigm in organic synthesis

“…The generated N-tosylmethylbenzamides 108 underwent an unusual substitution reaction in the presence of organocopper and organo-magnesium reagents to furnish N-(alkoxymethyl)benzamides 109 (Scheme 66). 79 Mechanistically, N-tosylmethylbenzamides 109 generated anion A in the presence of an organometallic reagent and eliminated tosylsulnate anion B, which attacked the imine and cyclized to generate acyloxaziridine intermediate D. Furthermore, the attack of the organometallic reagent at the oxaziridine oxygen furnished N-(alkoxymethyl)benzamides 110 (Scheme 67).…”

Bis(thiocarbamates): Synthesis and Substituent Effects on the Barrier to N‐CO Rotation

“…In addition, carbamate protecting groups are well known for the protection of primary and secondary amines . Among the different routes used for their synthesis, the addition of thiols or alcohols to isocyanates is the most common method . Recently, the synthesis of polythiourethanes has shown an increasing expansion primarily due to their successful industrial and commercial applications as high refractive index optical materials .…”

“…Recently, the synthesis of polythiourethanes has shown an increasing expansion primarily due to their successful industrial and commercial applications as high refractive index optical materials . Despite the enormous work carried out on polyurethane and polythiourethane , studies on monomer analogs (i.e., urethanes or diurethanes) are much less reported in the literature . This seems to be surprising since investigation of the structure and properties of the latter simple molecules would be much easier before polymerization than that undertaken on the more complicated polymer counterparts.…”

An Efficient Direct Access to Carbamates from Alcohols and TosMIC Mediated by Iodine in DMSO

“…13 The previous report by Ganem and co-workers for the synthesis of carbamates employing TosMIC involves a two-step process that requires low reaction temperature conditions. 14 Herein, we describe an efficient new strategy to carbamates from alcohols and TosMIC promoted by Scheme 1 Previous work and our approach for the synthesis of carbamates…”